US6372181B1 - Low cost, corrosion and heat resistant alloy for diesel engine valves - Google Patents
Low cost, corrosion and heat resistant alloy for diesel engine valves Download PDFInfo
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- US6372181B1 US6372181B1 US09/934,892 US93489201A US6372181B1 US 6372181 B1 US6372181 B1 US 6372181B1 US 93489201 A US93489201 A US 93489201A US 6372181 B1 US6372181 B1 US 6372181B1
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- alloy
- diesel engine
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01L—CYCLICALLY OPERATING VALVES FOR MACHINES OR ENGINES
- F01L3/00—Lift-valve, i.e. cut-off apparatus with closure members having at least a component of their opening and closing motion perpendicular to the closing faces; Parts or accessories thereof
- F01L3/02—Selecting particular materials for valve-members or valve-seats; Valve-members or valve-seats composed of two or more materials
Definitions
- the present invention relates generally to corrosion and heat resistant alloys and, more particularly, is directed to a Fe—Ni—Cr alloy useful for diesel engine components, primarily exhaust valves.
- the alloy features a favorable balance of low cost, high-temperature monotonic and fatigue strength, corrosion resistance, and metallurgical stability.
- the alloy of the present invention may also be usefully employed in the manufacture of other diesel engine parts such as, for example, exhaust train components which experience similarly aggressive environments.
- the aforementioned alloys exhibit some shortcomings.
- Pyromet® 31V features a relatively high Ni content and was also found to precipitate a potentially embrittling acicular alpha ( ⁇ )-Cr phase after extended exposures to service temperatures of 760° C. (1400° F.).
- the 40 Ni alloy is low cost but contains only moderate amounts of Cr, thus impairing corrosion resistance.
- the alloy seems to be prone to unwanted eta ( ⁇ )-phase (Ni 3 Ti) precipitation upon extended exposure harming ductility.
- alloy HI® 461 which features a dispersion of primary TiC carbides in addition to the customary gamma prime ( ⁇ ′)-strengthening. It was felt, however, that further performance enhancements at the same moderate cost level were still needed in order to achieve even further improvements in engine performance and reliability.
- the present invention is directed to an improved alloy particularly suited for diesel engine exhaust valves and the like which features an attractive balance of low cost, high-temperature monotonic and fatigue strength, corrosion and abrasion resistance, metallurgical stability, and ease of fabrication.
- the alloy according to the present invention is characterized by a composition in weight percent of about 0.15-0.65% C, 40-49% Ni, 18-22% Cr, 1.2-1.8% Al, 2.0-3.0% Ti, 0.9-7.8% Nb, not more than 1% Co and Mo each, the balance being Fe and inevitable impurities, whereby the Ti:Al ratio (wt. %) must not exceed 2:1, and the Nb:C ratio (wt. %) is adjusted to lie within the range of 6:1 and 12:1 (or 0.8:1 to 1.5:1 on an atomic basis).
- a further presently preferred Nb range is 0.9-6.5 wt. % with a Nb:C ratio of between 6:1 and 10:1 on a wt. % basis (or 0.8:1 to 1.3:1 on an atomic basis).
- Nb may be partially substituted for Ta on an equiatomic basis.
- the ratio of the combined atomic percentage (Nb+Ta) to C present should be adjusted to lie within the range of 0.8-1.5.
- the alloy may also contain certain elements essential for deoxidation/desulfurization and improved hot workability in the following amounts: up to 2.0% Mn, up to 0.01% B, and up to 0.3% Zr. Silicon additions up to 1.0 wt. % are also beneficial to improve the alloy's oxidation resistance.
- the C content is limited to 0.25-0.55%
- the Ni content is 42-48%
- the Cr content is 19-21%
- the Al content is 1.4-1.7%
- the Ti content is 2.3-2.7%
- the Nb content is 1.8-5.5%
- the balance being Fe and inevitable impurities
- the Nb:C weight % ratio is adjusted to lie within the range of 7:1 and 10:1, and the Ti:Al weight % ratio is less than or equal to 2:1.
- a still more preferred Nb range is about 2.5-3.0%.
- the microstructure of the alloy of the present invention features, even after extended exposures to valve operating temperatures in the vicinity of 760° C. (1400° F.), essentially a uniform dispersion of micron size Nb-rich primary MC type carbides, fine discrete Cr-rich secondary M 23 C 6 type carbides in the austenite grain boundaries, and submicroscopic intragranular ⁇ ′ precipitates. Moreover, the microstructure of a preferred embodiment of the invention features less than 5 vol. % of any acicular phase.
- the present invention further includes diesel engine valves, particularly exhaust valves, as well as other exhaust train components, manufactured from the above described alloy.
- FIG. 1 ( a ) is a graph of ultimate tensile strength versus temperature for Alloys 1-5 of the present invention and several comparative alloys of the prior art;
- FIG. 1 ( b ) is a graph of tensile elongation versus temperature for Alloys 1-5 of the present invention and several comparative alloys;
- FIG. 2 is a graph of rotating beam fatigue strength versus cycles to failure showing fatigue data for Alloys 1-5 of the present invention and several comparative alloys;
- FIG. 3 is a graph of hardness versus temperature for Alloy 2 of the present invention and two comparative alloys
- FIGS. 4 a - 4 c are bar graphs depicting hot salt corrosion attack on alloys of the present invention and several comparative alloys;
- FIGS. 5 a and 5 b are bar graphs showing Charpy impact strength of alloys of the invention and comparative alloys.
- FIG. 6 is a scanning electron photomicrograph of Alloy 2 of the invention after 2,500 hours' exposure to a temperature of 1400° F. (760° C.).
- the chemical composition of the alloy is limited as described below.
- Carbon (C) in the amounts present combines during melting with Nb and Ti to form (Nb,Ti)C-rich primary MC carbides.
- These primary carbides relatively uniformly disperse throughout the microstructure and provide primarily abrasion resistance in the alloy due to their hard, abrasive nature. If carbon is present in amounts of less than 0.15%, the volume fraction of these primary carbides is insufficient to cause the desired abrasion resistance. However, if carbon is present in amounts greater than 0.65%, the resulting carbides tend to cluster, thus impairing hot workability and valve surface quality.
- Nickel (Ni) stabilizes the austenitic matrix phase and is essential for the formation of the strengthening ⁇ ′ phase (Ni 3 (Al,Ti)) utilized to impart heat resistance on the alloy.
- Ni is, on a cost basis, a relatively expensive alloying element (in comparison with Fe) and, hence, limited to less than 49 wt. %.
- the lower bound of 40 wt. % is determined by metallurgical stability considerations, i.e., the increasing propensity of the alloy to form harmful TCP (topologically close packed) phases, in particular sigma ( ⁇ ) phase, upon extended service.
- Chromium (Cr) is of paramount importance in imparting high-temperature oxidation and corrosion resistance to the alloy. Controlled laboratory tests simulating hot salt corrosion in an engine environment have shown that a minimum amount of 18 wt. % Cr is needed to attain satisfactory corrosion resistance. When Cr is added in amounts greater than 22 wt. %, however, the alloy becomes prone to massive intragranular precipitation of acicular phases, ⁇ or ⁇ -Cr upon extended exposures to 760° C., thus harming ductility and toughness.
- Cr contents in the above defined range can also be used to promote the precipitation of discrete secondary grain boundary carbides of the M 23 C 6 type, thus increasing stress rupture strength.
- Aluminum (Al) is the primary hardening element leading in the above amounts present to the formation of ⁇ ′ (Ni 3 (Al,Ti)).
- ⁇ ′ Ni 3 (Al,Ti)
- Al contents below 1.2 wt. % the volume fraction of ⁇ ′ is too small to meet the monotonic and fatigue strength targets.
- Contents of Al greater than 1.8 wt. % result, however, in increasing hot workability problems when forming the valves.
- Titanium (Ti) is, next to Al, of utmost importance for the formation of ⁇ ′. Moreover, by virtue of increasing the anti-phase boundary energy of ⁇ ′, alloying with Ti also results in a stronger precipitate, thus improving the overall strength of the alloy. On the other hand, exceedingly large amounts of Ti lead to phase instability, i.e., the precipitation of eta ( ⁇ )-phase (Ni 3 Ti). This ⁇ -phase is generally considered harmful for ductility. Hence, the Ti:Al wt. % ratio is limited to 2:1. The total combined amount of hardener elements (Al+Ti) is adjusted to balance strength requirements with fabricability of the alloy.
- Nb niobium
- the primary purpose of alloying with niobium (Nb) is to cause precipitation of primary Nb-rich MC carbides.
- These Nb-rich carbides are more effective than Ti-rich MC carbides in increasing the abrasion resistance of the alloy owing to their higher hot hardness.
- the Nb content is carefully balanced against the C content.
- Nb:C weight ratios less than 6.5:1 or 6:1 (or 0.8:1 on an atomic basis) the primary carbides become increasingly Ti-rich, thus diminishing the positive effect on the abrasion resistance.
- Nb:C ratios greater than 12:1 or 1.5:1 on an atomic basis
- the uncombined Nb tends to overalloy the austenitic matrix, thus raising the solvus temperature of harmful TCP phases above the valve operating temperature.
- the Nb:C weight % ratio should reside within the range of 6:1 to 12:1 or within the range of 0.8:1 to 1.5:1 on an atomic basis.
- a presently preferred broad range for Nb is about 0.9 to 7.8 wt. %, with a preferred intermediate range of 0.9 to 6.5 wt. % Nb and a narrow range of 1.8 to 5.5 wt. % Nb, or a more narrow range of 2.5 to 3.0 wt. % Nb.
- Nb also improves the weldability of ⁇ ′-hardened superalloys and, likewise, increases corrosion resistance in sulfidizing environments, such as those encountered in diesel engines.
- Nb may be partially substituted for tantalum (Ta) on an equiatomic basis, cost permitting.
- Ta also strongly stabilizes the primary MC carbide and is surmised to be equally beneficial to hot hardness and abrasion resistance.
- Co Co
- molybdenum (Mo) at levels exceeding 1 wt. % impairs corrosion resistance in sulfur-containing environments at valve operating temperatures.
- Mn manganese
- B Boron
- zirconium Like boron, zirconium (Zr) is also effective in improving the hot workability and creep rupture strength if present in small amounts. Zr in excessive amounts, however, harms hot workability.
- Si not more than 1.0 wt. %
- Si is an element effective in improving the oxidation resistance of the alloy.
- excessive additions of Si deteriorate the ductility of the material.
- Iron (Fe) is essentially a matrix-forming element and comprises the balance of the alloy including unavoidable or incidental impurities and trace elements in residual amounts.
- a more narrow, presently preferred alloy composition according to the invention consists essentially of in % by weight: 0.25-0.55% C, 42-48% Ni, 19-21% Cr, 1.4-1.7% Al, 2.3-2.7% Ti, 1.8-5.5% Nb, the balance essentially Fe and incidental impurities, and wherein the Nb:C weight % ratio is about 7:1 to 10:1.
- the Nb range may be further narrowed to about 2.5-3.0 wt. %.
- Alloy 1 through Alloy 5 Five alloys formulated according to the present invention, designated Alloy 1 through Alloy 5, and two comparative alloys mimicking HI® 461 and the 40 Ni alloy (designated “HI 461” and “40 Ni”, respectively), were vacuum induction melted and cast into 22 kg (50 lb.) ingots. A conventional Ca+Mg deoxidation practice was used. The chemical compositions of the alloys are shown below in Table 1.
- FIGS. 1 a and 1 b Room temperature and elevated temperature tensile tests were conducted to assess the strength and ductility potentials of the alloys. The results of these tests are graphically depicted in FIGS. 1 a and 1 b.
- the tensile strength of the alloys of the present invention is of the same magnitude as that of the comparative alloys.
- the same is true for the ductility, i.e., tensile elongation reported in FIG. 1 b .
- the ductility minimum observed in the vicinity of 760° C. (1400° F.) is typical of many superalloys.
- Elevated temperature high-cycle rotating beam fatigue tests at 760° C. (1400° F.) to establish the fatigue strength limit at 10 8 cycles are reported in FIG. 2 .
- the cycles were carried out under full stress reversal.
- S—N curves for 23-8N, 21-4N, Pyromet® 31V and alloy 751/NIMONIC® alloy 80A as obtained from the literature are superimposed.
- This test is generally considered a benchmark test by engine manufacturers.
- An equivalent to enhanced fatigue performance of the alloys of the present invention over the stainless steels, HI® 461 and the 40 Ni alloy and even Pyromet® 31V is apparent.
- the performance level of the high cost Ni-base superalloys like alloy 751 could not be met with the low cost alloy of this invention. This, however, was not the aim of the present invention.
- Hot hardness tests up to 760° C. (1400° F.) using a Rockwell A tester and converting the hardness numbers to Rockwell C are reported in FIG. 3 to rank the alloys in terms of their abrasion resistance.
- the highest hot hardness was measured on an alloy of this invention, thus demonstrating a superior abrasion resistance of this alloy over the comparative alloys. It can, hence, be expected that hardfacing the alloy of this invention will not be necessary.
- Hot salt corrosion tests (an 80-hour standard, and a 250-hour aggravated test) in a mixture of CaSO 4 :BaSO 4 :Na 2 SO 4 :C in a ratio of 10:6:2:1, respectively, at a temperature of 870° C. (1598° F.) are reported in FIGS. 4 a , 4 b and 4 c.
- the longer the bar graphs on FIGS. 4 a-c the poorer the corrosion resistance of the particular alloy tested.
- Each alloy tested is listed in the box appearing on each of FIGS.
- alloy HI 461 is identified with the letter “(A)”, alloy 40 Ni as “(B)”, alloy 1 of the invention as “(C)”, alloy 2 of the invention as “(D)”, and alloy 751 as “(E)”.
- alloys 2-5 of the present invention are identified as follows: alloy 2 as “(D)”, alloy 3 as “(G)”, alloy 4 as “(H)” and “(I)” (duplicate test) and alloy 5 as “(J)”.
- the samples were recoated at 80 hour intervals. This is one of the tests believed to be crucial as a measure of valve performance. In the 80-hour, standard test depicted in FIG.
- both the alloys of this invention (C) and (D) and the comparative alloys (A) and (B) showed, presumably due to their higher Fe content, significantly less attack than the high Ni alloy 751 (E). Further discrimination resulted from the aggravated 250-hour tests of FIGS. 4 b and 4 c . In this aggravated test, the superior corrosion resistance of the alloys of the present invention, especially of the alloys of the preferred embodiment, became very apparent.
Abstract
Description
TABLE 1 |
Chemical composition (in wt. %) of examples of the alloy of the |
invention and comparative alloys |
Alloy | Fe | Ni | Cr | Al | Ti | Nb | C | Nb: |
1 | bal. | 47.1 | 19.9 | 1.5 | 2.5 | 1.6 | 0.17 | 9.4 |
2 | bal. | 47.0 | 19.9 | 1.5 | 2.5 | 2.5 | 0.28 | 8.9 |
3 | bal. | 46.6 | 20.2 | 1.5 | 2.4 | 2.4 | 0.27 | 8.8 |
4 | bal. | 45.9 | 20.3 | 1.6 | 2.2 | 3.1 | 0.44 | 7.1 |
5 | bal. | 44.7 | 20.1 | 1.7 | 2.5 | 3.7 | 0.53 | 7.0 |
|
bal. | 47.0 | 17.9 | 1.2 | 4.2 | <0.1 | 0.31 | <0.32 |
40 Ni | bal. | 41.1 | 16.0 | 0.9 | 2.9 | 0.8 | 0.02 | 40.0 |
Claims (12)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US09/934,892 US6372181B1 (en) | 2000-08-24 | 2001-08-22 | Low cost, corrosion and heat resistant alloy for diesel engine valves |
Applications Claiming Priority (3)
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---|---|---|---|
US22770000P | 2000-08-24 | 2000-08-24 | |
US66348900A | 2000-09-18 | 2000-09-18 | |
US09/934,892 US6372181B1 (en) | 2000-08-24 | 2001-08-22 | Low cost, corrosion and heat resistant alloy for diesel engine valves |
Related Parent Applications (1)
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US66348900A Continuation-In-Part | 2000-08-24 | 2000-09-18 |
Publications (2)
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US6372181B1 true US6372181B1 (en) | 2002-04-16 |
US20020044882A1 US20020044882A1 (en) | 2002-04-18 |
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US09/934,892 Expired - Lifetime US6372181B1 (en) | 2000-08-24 | 2001-08-22 | Low cost, corrosion and heat resistant alloy for diesel engine valves |
Country Status (8)
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US (1) | US6372181B1 (en) |
EP (1) | EP1313888B1 (en) |
JP (1) | JP3905034B2 (en) |
AT (1) | ATE267271T1 (en) |
AU (1) | AU2001285211A1 (en) |
CA (1) | CA2420346A1 (en) |
DE (1) | DE60103410T2 (en) |
WO (1) | WO2002016661A2 (en) |
Cited By (14)
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US20080008617A1 (en) * | 2006-07-07 | 2008-01-10 | Sawford Maria K | Wear resistant high temperature alloy |
US20080163957A1 (en) * | 2007-01-04 | 2008-07-10 | Ut-Battelle, Llc | Oxidation resistant high creep strength austentic stainless steel |
US20080292489A1 (en) * | 2007-01-04 | 2008-11-27 | Ut-Battelle, Llc | High Mn Austenitic Stainless Steel |
US20080304996A1 (en) * | 2007-01-04 | 2008-12-11 | Ut-Battelle, Llc | High Nb, Ta, and Al Creep- and Oxidation-Resistant Austenitic Stainless Steels |
US20090081073A1 (en) * | 2007-06-07 | 2009-03-26 | Celso Antonio Barbosa | Alloys with high corrosion resistance for engine valve applications |
US20090081074A1 (en) * | 2007-06-07 | 2009-03-26 | Celso Antonio Barbosa | Wear resistant alloy for high temprature applications |
US20150354039A1 (en) * | 2012-12-28 | 2015-12-10 | The Japan Steel Works, Ltd. | Fe-ni-based alloy having excellent high-temperature characteristics and hydrogen embrittlement resistance characteristics, and method for producing the same |
US9540714B2 (en) | 2013-03-15 | 2017-01-10 | Ut-Battelle, Llc | High strength alloys for high temperature service in liquid-salt cooled energy systems |
US9605565B2 (en) | 2014-06-18 | 2017-03-28 | Ut-Battelle, Llc | Low-cost Fe—Ni—Cr alloys for high temperature valve applications |
US20170130603A1 (en) * | 2015-11-11 | 2017-05-11 | Mitsubishi Hitachi Power Systems, Ltd. | Austenite steel, and austenite steel casting using same |
US9683280B2 (en) | 2014-01-10 | 2017-06-20 | Ut-Battelle, Llc | Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems |
US9683279B2 (en) | 2014-05-15 | 2017-06-20 | Ut-Battelle, Llc | Intermediate strength alloys for high temperature service in liquid-salt cooled energy systems |
US11479836B2 (en) | 2021-01-29 | 2022-10-25 | Ut-Battelle, Llc | Low-cost, high-strength, cast creep-resistant alumina-forming alloys for heat-exchangers, supercritical CO2 systems and industrial applications |
US11866809B2 (en) | 2021-01-29 | 2024-01-09 | Ut-Battelle, Llc | Creep and corrosion-resistant cast alumina-forming alloys for high temperature service in industrial and petrochemical applications |
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WO2017184778A1 (en) | 2016-04-20 | 2017-10-26 | Arconic Inc. | Fcc materials of aluminum, cobalt and nickel, and products made therefrom |
KR20180115344A (en) | 2016-04-20 | 2018-10-22 | 아르코닉 인코포레이티드 | FCC materials made of aluminum, cobalt, iron, and nickel, and products made therefrom |
CN111074131B (en) * | 2019-12-26 | 2021-07-20 | 西北工业大学 | Thermal mechanical treatment method of eutectic high-entropy alloy |
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2001
- 2001-08-22 US US09/934,892 patent/US6372181B1/en not_active Expired - Lifetime
- 2001-08-23 AU AU2001285211A patent/AU2001285211A1/en not_active Abandoned
- 2001-08-23 JP JP2002522331A patent/JP3905034B2/en not_active Expired - Fee Related
- 2001-08-23 WO PCT/US2001/026277 patent/WO2002016661A2/en active IP Right Grant
- 2001-08-23 EP EP01964346A patent/EP1313888B1/en not_active Expired - Lifetime
- 2001-08-23 AT AT01964346T patent/ATE267271T1/en active
- 2001-08-23 CA CA002420346A patent/CA2420346A1/en not_active Abandoned
- 2001-08-23 DE DE60103410T patent/DE60103410T2/en not_active Expired - Lifetime
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US20080008617A1 (en) * | 2006-07-07 | 2008-01-10 | Sawford Maria K | Wear resistant high temperature alloy |
US7651575B2 (en) * | 2006-07-07 | 2010-01-26 | Eaton Corporation | Wear resistant high temperature alloy |
US7754305B2 (en) | 2007-01-04 | 2010-07-13 | Ut-Battelle, Llc | High Mn austenitic stainless steel |
US20080163957A1 (en) * | 2007-01-04 | 2008-07-10 | Ut-Battelle, Llc | Oxidation resistant high creep strength austentic stainless steel |
US20080292489A1 (en) * | 2007-01-04 | 2008-11-27 | Ut-Battelle, Llc | High Mn Austenitic Stainless Steel |
US20080304996A1 (en) * | 2007-01-04 | 2008-12-11 | Ut-Battelle, Llc | High Nb, Ta, and Al Creep- and Oxidation-Resistant Austenitic Stainless Steels |
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US9994938B2 (en) * | 2012-12-28 | 2018-06-12 | The Japan Steel Works, Ltd. | Fe-Ni-based alloy having excellent high-temperature characteristics and hydrogen embrittlement resistance characteristics, and method for producing the same |
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US20170130603A1 (en) * | 2015-11-11 | 2017-05-11 | Mitsubishi Hitachi Power Systems, Ltd. | Austenite steel, and austenite steel casting using same |
US10415423B2 (en) * | 2015-11-11 | 2019-09-17 | Mitsubishi Hitachi Power Systems, Ltd. | Austenite steel, and austenite steel casting using same |
US11479836B2 (en) | 2021-01-29 | 2022-10-25 | Ut-Battelle, Llc | Low-cost, high-strength, cast creep-resistant alumina-forming alloys for heat-exchangers, supercritical CO2 systems and industrial applications |
US11866809B2 (en) | 2021-01-29 | 2024-01-09 | Ut-Battelle, Llc | Creep and corrosion-resistant cast alumina-forming alloys for high temperature service in industrial and petrochemical applications |
Also Published As
Publication number | Publication date |
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WO2002016661A2 (en) | 2002-02-28 |
ATE267271T1 (en) | 2004-06-15 |
WO2002016661A3 (en) | 2002-06-06 |
EP1313888B1 (en) | 2004-05-19 |
DE60103410D1 (en) | 2004-06-24 |
AU2001285211A1 (en) | 2002-03-04 |
JP3905034B2 (en) | 2007-04-18 |
JP2004512428A (en) | 2004-04-22 |
DE60103410T2 (en) | 2005-06-30 |
US20020044882A1 (en) | 2002-04-18 |
CA2420346A1 (en) | 2002-02-28 |
EP1313888A2 (en) | 2003-05-28 |
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